Production of naphthalene derivatives



Patented Jan. 19, 1932 UNITIEZD' T i N T- Q F C I FILIP Knees, or Mmmmmmarmm mama or timwmsmsmommn RHINE f GERMANY; l ssieiwonro GENERAL 1A in "Linn wos zs,'mc.,;or New vYORK,

. Y., A' CORPORATION or. DELAWABE 'reonuo'rron ornnrnmrmnnnnlnjmrvnrrvns if no Drawing. Application iil'ed March 31, i930, Serial No. demand in Gamay A ril 5, 192a The present invention relates to theyproduction of naphthalene. derivatives, from naphthalenes substituted in the l-positionibyi an alkyl or aralkyl group by -mean s of. carboxylic acid ohlorid ,v

We have foundthat derivatives ofnapha halene which are Veryvaluable industrially are obtained by allowing carboxylic acid chlorides to act according to the Friedel- Crafts reaction on a naphthalene substi= tuted in the l-position by an alkyl or an ax alkyl group and having a free l-pos'ition, "or

substitution products thereof, such 'as [for example halogenoderivatives. v In this ner the new l-alkyl and 1-araIkyLnaphtha l'ene-l-keton'es are obtained. y j

By treating the ketones thus obtained with oxidizing agents the aralkylnaphthalene ketones in case an aromatic 'earboxylie acid chloride has been u'sedfor' thecondfensatilon; yield'L l-diketones, in case an aliphatieean boxylie acid chloride has been em loyed the corresponding l -aroyl -4 -'carboxylicj" acids. Likewise from aliphatic li-alkylna 'hthalene ketones the corresponding 1-alky naphtha lene-e-carboxylic acids and on furtherjoxidation 1.4-naphthalene-dicarboxylic acids are obtained. Acid as Well as alkaline 0Xidizingagents may .beemployed, for example alkali metal hypochlorite solution-sand nitric acid the latter being prefer-ably employed for the oxidation of the alkyl groupsto'tcarboxe ylic acid groups. The products thus prepared may be employed'amcng otherpur poses as initial materials tor the manufacture of dyestufis.

The following exainples will. further illus trate the nature of this invention but the invention is not restricted to these exainples. The parts are by weight; I I

' Example 1 160 parts of owdereaammimiia 151 10565 are introduced at 5 G. into asolution o'f 218 parts of l-benzylnaphthalene and 145;parts ofben'zeylchleride in 520 part of benzene while stirring continuously. Hydregen'ehloride is evolved and the temperature rises to about 30 After-"stirring forts-ore 2 to 3 hours without cooling;- wherebyv the temperature gradually falls again to rated and dried with sodium carbonate. By distilling off tl'ieleenzene at temperatures up to about 150. G.v (measured in the liquid).

crude 4;-benzoyl-l-benzylnaphthalene isob tained. r

In order toobtainfithe product quite pure; the oily productobtained may for example be distilled in -vacuo ,-thecrude distillate then being mixed with about, the same volume of ether Crystallization very rapidlytakes place, and'the pure 4a-benzoyl l benzylnaphe j thalene separates out in the form of white crystals having a melting; point of about 110 C. T

I 1 Example? partsof 4-benzoyl-vl-benzylnaphthalene are boiled under'a refluit condenser With400 parts'of nitric acid of 40"B. strength and SOOpartsfof' Water untilthe evolution or brown gaseous oxides of'n-itr'ogen subsides.

The pale yellow resin which readily solidifies is then separated oil, washed with water and freed fromsinall amounts of alkalisoluble i'1n p11ritiesfby' boiling up with caustic soda solution. Tljie 1.4-dibenzoylnaphthalene thus obtained is'a1ready1suifieient1y pure for most purposes]; inorder to obtain it in mperfectly purestateit may be crystallized for example ironiralcohol. From this solvent it crystallizesin wl'iite'o'rystals having a melting point o'fabout 10.6 ;C.. It is veryva-luable industrially and may readily be converted for exampleinto isodibenzpyrenequinone.

' Ewample 1400 partsipffground alliininium chlori'gile are 7 introduced 'wliile stirring continuou sl into a solution 015.631 parts o f 4";-elilorbenzy 1-naphthaleneaiidf386 parts of benzoyl ehloride in 1560 parts at benzene which has. been oeoled tob? 0., sothat the-temperature rises to about frorn l'l' to20 C In'this'manner a yellow red solution is" formed with the evolution -:ofi,hydroehleric acid." The $6111:-

tion is stirred for from 2 to 3 hours and is then poured into water in order to decompose the aluminium chloride double compound. The benzene solution is separated oft and is dried with sodium carbonate. In order to purify the crude product it is distilled, pref erably in vacuo, and the main fraction, of high boilin point, is crystallized from ether. The pure v4-benzoyl-a-chlorbenzyl 1-naphthalene forms white crystalshaving a melt ing point of about 123 C. 4-chlor-1.4- dibenzoylnaphthalene having melting point of about 118 C(may be obtained therefrom by oxidation.

When p-chlorbenzoyl chloride is employed in this example instead of benzoyl'chloride, 1 p 'chlorbenzoyl -1 p chlorbenzylnaphtha lene, and by oxidation 1.4-di-g9-chlorbenzoylnaphthalene, are respectively'obtained.

I Ewample 4 100 parts of ground aluminiumrchloride are introduced while stirring continuously into a solution cooled to 5 C. of 109 parts of 1-benzylnaphthalene and 59 parts of acetyl chloride in 390 parts of benzene, so'that the temperature rises to from about to 22 C. A yellow red solution is formed with the evolution of hydrochloric acid. The solution is stirred in'water, the benzene solution separated oiland dried with sodium carbonate. In order to obtain the new ketone in a state of purity the'crude product is distilled, preferably in vacuo. The main fraction, of high boiling point, is crystallized from alcohol. The melting point of the pure l-acetyl-l-benzylnaphthalene is about -7 8 C. By oxidizing this under suitable. conditions, for example with dilute nitric acid, 4-9 l-benzoyl--naphthoic acid having a melting point of about 184 C. is obtained.

Example 5 pa-rts of 1-methylnaphthyltphenylketone, obtainable by the action of benzoyl chloride on l-methyl-naphthalene according to the Friedel-Crafts reaction, are boiled with 750 parts of 20 per cent nitric acid until the evolution of brown gaseous oxideslof nitrogen has subsided. The yellow resinous reaction product is then separated and if desired further purified by dissolving in dilute caustic soda solution, the solution being clarified by heating with a little sodium hypochlorite. The solution is filtered and the l-benzoyl-l-naphthoic acid;v is precipitated with dilute hydrochloric acid. The

product melts at about 184 C. after'having been crystallizedfrom glacial acetic acid. i Ewcmnple 6 y r 75 parts of 1-niethylnaphthyd-Hnethylketone, obtainable by the action of acetyl chloride on l-methylnaphthalene according 5. to the Friedel-Crafts reaction, are heated to mercury recovered separately. The crystalphenyl ketone.,

solution of sodium l-methyl l-naphthoate is obtained. The solution is filtered and the 1-niethyl-4-naphthoic acid is precipitated with hydrochloric acid. In the pure state it forms, white crystals having a melting point of about 165C.

It 1500 parts of 20 per cent nitric acid be employed'insteadof the solution of sodium hypochlorite and the whole be boiled under a reflux condenser until the evolution of brown gaseous oxides of nitrogen subsides, the

known .naphthalene-lA-dicarboxylic acid is obtainedw r Example '7 800 parts of pulverized aluminium chloride are introduced, while stirring and cooling with ice to between 5 and 10 0., into a solutionof 710 parts of a-methylnaphthalene and 703 parts of benz'oylchloride in 2340 parts of benzene. Hydrogen chloride is evolved and the temperature rises slowly to between 20 and 25 C. Stirring is continued for from 2 to 3 further hours at the said temperature, the whole being then poured" onto ice, the benzene solution separated, dried by means of anhydrous soda and the excess of benzene distilled off. In case the remaining oil does not crystallize it is distilled in Vacuo and that part, boiling between 270 and 280 C. under a pressure of 37 millimeters lizingproduct is pure ;1-methylnaphthyl-lm5 Ewample 8 400 parts of aluminium ch'loride are introduced, while cooling to10 0., into a solution of 196 part-sot acetylchloride in 200 parts of carbon disulphide. Thereupon 284 a parts of wmethylnaphthalene are run in at between 10 and 20-C., the reaction mixture being stirred for three hours at the said temperature. The yellow crystal pulp obtained is filtered off, washed with carbon disulphide and the residue decomposed-in the usual manner by means of water. The oil thus obtained is dried anddistilled fractionally. The part passing over at between about 323 to327 (3., is pure l-methylnaphthyllmethyl ketone. 3 I

. 1. A process for the'production of naph- "consisting of'alkylanda ralkyl radicles, and

having a free iposition with a carboxylic acid chloride according to the Friedel-C-rafts reaction.

2A process for the production of naphthalene derivatives which comprises acting on 'l-benzylnaphthalene with benzoyl chlo-' 1 ride according to the Friedel Crafts reaction.

our hands.

3. As new articles of m'a'nufacturc naphthalene derivatives corresponding to the formula: y

V o= i Y in which X stands for a substituentselected from the group consisting of .alkyl and aralkyl radic1es,.and Y stands for an aliphaticor aromatic radicle. f e 4. As new articles of manufacture naph thalene derivatives corresponding to the 'formula:

in which Y stands for an aliphatic or aromatic radicle.

5. As new articleof manufacture -benzoyl-1-benzyl-naphtha1ene.

In testimony whereof wehave hereunto set FILIP KACER.

ARTUR KRAUSE... 

